1. Field of the Invention
The invention relates to blends of nylon homopolymers and copolymers with certain other polymers. More particularly, the invention pertains to blends of nylon 6 and its copolymers with certain other polymers useful to form films having high miscibility, high clarity and good processability.
2. Description of the Prior Art
It is well known that miscibility of polymer-polymer blends is very rare. This is because most polymer pairs with dissimilar structures invariably form phase-separated immiscible blends due primarily to the unfavorable intersegmental incompatibility. It is also known that nylons are especially incompatible and immiscible with other polymers due to a hydrogen bonded polyamide backbone. Only a limited type of amorphous nylons having a polyamide backbone are known to exhibit some degree of miscibility with other nylons having a similar polyamide backbone, for example nylon 6I/6T with nylon 6.
It would be desirable to provide blends of nylons with other polymers, preferably blends which are miscible.
The invention provides a polymeric composition comprising a blend of at least one polyamide component and at least one poly(hydroxyamino ether) component.
The invention also provides a polymeric film formed from a polymeric composition comprising a blend of at least one polyamide component and at least one poly(hydroxyamino ether) component.
The polymer composition also preferably includes an oxygen scavenger composition, such as an oxidizable polydiene, and a metal salt catalyst, such as a metal carboxylate salt. It is also desired that polymer compositions of this invention comprise a nanometer scale dispersed platelet type clay to further augment their barrier and oxygen scavenging properties. Such clays are normally referred to as nanoclays and they are normally composed of organo-ammonium cation exchanged montmorillonite or hectorite type smectitic clays.
The invention further provides a polymeric film formed from a polymeric composition comprising a blend of at least one polyamide component, at least one poly(hydroxyamino ether) component, optionally at least one platelet type organoclay in nanometer scale fine dispersion, and optionally at least one oxidizable polydiene, or at least one metal salt catalyst, or both.
The invention still further provides shaped articles formed from the compositions of the invention.
It has unexpectedly been found that nylon 6 and its copolymers form very homogenous, miscible blends when melt compounded with poly(hydroxyamino ether) polymers, combining the advantages of both polymers. Particularly, poly(hydroxyamino ether) polymers, such as those described in U.S. Pat. No. 5,731,094, are known to exhibit good oxygen and carbon dioxide gas barrier properties, but have poor melt processability and poor heat resistance due to lack of crystallinity, and exhibit low Tg. On the other hand, nylons are known to have poor gas barrier properties, but good melt processability and heat resistance. This miscible blend has been found to substantially improve the gas barrier properties of nylon, particularly at high humidity levels, while retaining good melt processability. Films formed from such blends also exhibit high clarity and a reduced or controlled nylon crystallization rate, which is particularly beneficial for in blown film processing, coinjection stretch blowmolding and large-diameter monofilament spinning.
The polymeric composition of the claimed invention relates most broadly to blends of nylon homopolymers and/or nylon copolymers with poly(hydroxyamino ether) polymers. Poly(hydroxyamino ether) polymers are epoxy-based thermoplastics produced through the reaction of liquid epoxy compounds and primary amines. They exhibit excellent barrier properties to atmospheric gases, good optical clarity, good adhesion to a variety of substrates, as well as good melt strength and mechanical behavior. The poly(hydroxyamino ether) polymers useful herein are described by the following formula: 
wherein Ar=p- or m-phenylene; alkyl substituted p- or m-phenylene; 4,4xe2x80x2-isopropylidene-bis-phenylene; or 4,4xe2x80x2-oxy-bis-phenylene;
R=alkyl; xcfx89-hydroxyalkyl; aryl; o-, m- or p-hydroxyaryl xcfx89-hydroxy-(polyalkyleneoxy) alkyl; or xcfx89-alkoxy-(polyalkyleneoxy ) alkyl;
and n is an integer from about 5 to about 1000.
A preferred poly(hydroxyamino ether) is derived from a 1:1 polyaddition reaction of an aryldiglycidyl ether and monoethanolamine, represented by the formula: 
wherein Ar=p- or m-phenylene; alkyl substituted p- or m-phenylene; 4,4xe2x80x2-isopropylidene-bis-phenylene; or 4,4xe2x80x2-oxy-bis-phenylene;
and n is an integer from about 5 to about 1000.
Another preferred poly(hydroxyamino ether) component comprises a polyadduct of monoethanolamine with resorcinol diglycidyl ether or bisphenol A-diglycidyl ether or a combination thereof. Other useful poly(hydroxyamino ether) polymers may be found in U.S. Pat. Nos. 5,275,853 and 5,731,094.
Blended together with the poly(hydroxyamino ether) polymers are nylon homopolymers and/or nylon copolymers. Suitable nylons within the scope of the invention non-exclusively include homopolymers or copolymers selected from aliphatic polyamides and aliphatic/aromatic polyamides having a molecular weight of from about 10,000 to about 100,000. General procedures useful for the preparation of polyamides are well known to the art. Such include the reaction products of diacids with diamines. Useful diacids for making polyamides include dicarboxylic acids which are represented by the general formula:
HOOCxe2x80x94Zxe2x80x94COOH
wherein Z is representative of a divalent aliphatic radical containing at least 2 carbon atoms, such as adipic acid, sebacic acid, octadecanedioic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, and glutaric acid. The dicarboxylic acids may be aliphatic acids, or aromatic acids such as isophthalic acid and terephthalic acid. Suitable diamines for making polyamides include those having the formula:
H2N(CH2)nNH2
wherein n has an integer value of 1-16, and includes such compounds as trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, hexadecamethylenediamine, aromatic diamines such as p-phenylenediamine, 4,4xe2x80x2-diaminodiphenyl ether, 4,4xe2x80x2-diaminodiphenyl sulphone, 4,4xe2x80x2-diaminodiphenylmethane, alkylated diamines such as 2,2-dimethylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4 trimethylpentamethylenediamine, as well as cycloaliphatic diamines, such as diaminodicyclohexylmethane, and other compounds. Other useful diamines include heptamethylenediamine, nonamethylenediamine, and the like.
Useful polyamide homopolymers include poly(4-aminobutyric acid) (nylon 4), poly(6-aminohexanoic acid) (nylon 6, also known as poly(caprolactam)), poly(7-aminoheptanoic acid) (nylon 7), poly(8-aminooctanoic acid)(nylon 8), poly(9-aminononanoic acid) (nylon 9), poly(10-aminodecanoic acid) (nylon 10), poly(11-aminoundecanoic acid) (nylon 11), poly(12-aminododecanoic acid) (nylon 12), nylon 4,6, poly(hexamethylene adipamide) (nylon 6,6), poly(hexamethylene sebacamide) (nylon 6,10), poly(heptamethylene pimelamide) (nylon 7,7), poly(octamethylene suberamide) (nylon 8,8), poly(hexamethylene azelamide) (nylon 6,9), poly(nonamethylene azelamide) (nylon 9,9), poly(decamethylene azelamide) (nylon 10,9), poly(tetramethylenediamine-co-oxalic acid) (nylon 4,2), the polyamide of n-dodecanedioic acid and hexamethylenediamine (nylon 6,12), the polyamide of dodecamethylenediamine and n-dodecanedioic acid (nylon 12,12) and the like. Useful aliphatic polyamide copolymers include caprolactam/hexamethylene adipamide copolymer (nylon 6,6/6), hexamethylene adipamide/caprolactam copolymer (nylon 6/6,6), trimethylene adipamide/hexamethylene azelaiamide copolymer (nylon trimethyl 6,2/6,2), hexamethylene adipamide-hexamethylene-azelaiamide caprolactam copolymer (nylon 6,6/6,9/6) and the like. Also included are other nylons which are not particularly delineated here.
Aliphatic polyamides used in the practice of this invention may be obtained from commercial sources or prepared in accordance with known preparatory techniques. For example, nylon 6 can be obtained from Honeywell International Inc., Morristown, N.J. under the trademark CAPRON(copyright).
Exemplary of aliphatic/aromatic polyamides include poly(tetramethylenediamine-co-isophthalic acid) (nylon 4,I), polyhexamethylene isophthalamide (nylon 6,I), hexamethylene adipamide/hexamethylene-isophthalamide (nylon 6,6/6I), hexamethylene adipamide/hexamethyleneterephthalamide (nylon 6,6/6T), poly (2,2,2-trimethyl hexamethylene terephthalamide), poly(m-xylylene adipamide) (MXD6), poly(p-xylylene adipamide), polyhexamethylene terephthalamide (nylon 6,T), poly(dodecamethylene terephthalamide), polyamide 6I/6T, polyamide 6/MXDT/I, polyamide MXDI, polyamide MXDT, polyamide MXDI/T, polyhexamethylene naphthalene dicarboxylate (nylon 6/6N), polyamide 6N/6I, polyamide MXDT/MXDI and the like. Blends of two or more aliphatic/aromatic polyamides can also be used. Aliphatic/aromatic polyamides can be prepared by known preparative techniques or can be obtained from commercial sources. Other suitable polyamides are described in U.S. Pat. Nos. 4,826,955 and 5,541,267.
Preferred polyamides include nylon 6, nylon 6,6, nylon 6/66, nylon 66/6, nylon 6I/6T, nylon MXDI/T, as well as mixtures of the same. Of these, nylon 6 is most preferred, alone or in combination with nylon 6/66.
In the preferred embodiment of the invention, the polyamide component comprises from about 1% to about 99% by weight of the blend, more preferably from about 30% to about 95% by weight of the blend and most preferably from about 60% to about 90% by weight of the blend. In the preferred embodiment of the invention, the poly(hydroxyamino ether) component comprises from about 1% to about 99% by weight of the blend, more preferably from about 5% to about 70% by weight of the blend and most preferably from about 10% to 40% by weight of the blend.
The polymer composition of the invention also preferably contains at least one functional, oxidizable polydiene which serves as an oxygen scavenger, which is preferably dispersed as small particles which are compatible with and substantially uniformly distributed throughout the polymer composition. It must be noted that the nylon/polyhydroxyether polymer blend itself is not oxidizable under the ambient conditions of use of these materials as barrier packaging articles. Hence an oxidizable polydiene is used as the oxygen scavenger in the compositions of this invention. Preferably the oxidizable polydiene comprises an anhydride or epoxy functionality such that it reacts with the amine end group of the nylon used or the hydroxyl groups on the polyhydroxyamino ether used in the blend. Preferred functional polydienes include functional polyalkadiene oligomers which can have the following general structure: 
where R1, R2, R3 and R4 can be the same or different and can be selected from hydrogen (xe2x80x94H) or any of the lower alkyl groups (methyl, ethyl, propyl, butyl, etc.). Illustrative of the backbone structure are polybutadiene (1,4 or 1,2 or mixtures of both), polyisoprene (1,4 or 3,4), poly 2,3-dimethyl butadiene, polyallene, poly 1,6-hexatriene, epoxy functionalized, maleic anhydride grafted or copolymerized polybutadiene (1,4 and/or 1,2), epoxy functionalized polyisoprene, and maleic anhydride grafted or copolymerized polyisoprene.
A preferred oxygen scavenger includes a polybutadiene, particularly an epoxy or anhydride functional polybutadiene oligomer. The oxygen scavenger is preferably present in the polymer composition as a large number of small particles. The molecular weight of the functional polydiene oligomer preferably ranges from about 500 about to 10,000, preferably from about 750 to about 3000 and most preferably from about 1000 to about 2000. If included, it is preferably present in the overall composition in an amount of from about 0.1% to about 10% by weight, more preferably from about 1% to about 10% and most preferably from about 2% to about 5%. The functional, oxidizable polydiene is preferably present in the form of particles whose average particle size is in the range of from about 10 nm to about 5000 nm, and wherein the particles are substantially uniformly distributed throughout the polymer composition.
The polymer composition also preferably further comprises a metal salt catalyst such as a metal carboxylate salt catalyst. Suitable metal carboxylate salt catalysts have a counterion which is an acetate, stearate, propionate, hexanoate, octanoate, benzoate, salicylate, cinnamate, and combinations thereof. Preferably the metal carboxylate salt catalyst is a cobalt, copper or ruthenium, acetate, stearate, propionate, hexanoate, octanoate, benzoate, salicylate or cinnamate, or combinations thereof. The preferred metal carboxylate is cobalt, ruthenium or copper carboxylate. Of these the more preferred is a cobalt, such as cobalt stearate, or copper carboxylate and the most preferred is cobalt carboxylate. If included, it is present in the overall composition in an amount of from about 0% to about 1% by weight, preferably from about 0.001% to about 0.5% and more preferably from about 0.005% to about 0.1%. The most preferred range is from about 0.01% to about 0.05%.
In the preferred embodiment of the invention, the composition further comprises at least one optional platelet type organoclay in nanometer scale fine dispersion, known in the art as a nanoclay. Suitable clays are described in U.S. Pat. No. 5,747,560, which is incorporated herein by reference. Preferred clays non-exclusively include a natural or synthetic phyllosilicate such as montmorillonite, hectorite, vermiculite, beidilite, saponite, nontronite or synthetic flouromica, which has been cation exchanged with a suitable organoammonium salt. The preferred clay is montmorillonite, hectorite or synthetic flouromica. The more preferred clay is the montmorillonite or hectorite. The most preferred clays are alkylammonium-complexed montmorillonite nanoclay and 12-aminododecanoic acid-complexed montmorillonite nanoclay. The preferred organoammonium cation for treating the clay is N,Nxe2x80x2,Nxe2x80x3,Nxe2x80x2xe2x80x3 Bis(hydroxyethyl), methyl, octadecyl ammonium cation or xcfx89-carboxy alkylammonium cation, i.e., the ammonium cation derived such xcfx89-aminoalkanoic acids as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid. The preferred fine dispersions of nanometer scale silicate platelets are obtained either via an in-situ polymerization of polyamide forming monomer(s) or via melt compounding of polyamide in the presence of the organoammonium salt treated clay. The clay has an average platelet thickness in the range of from about 1 nm to about 100 nm and an average length and average width each in the range of from about 50 nm to about 500 nm. If included, it is present in the overall composition in an amount of from about 0% to about 10% by weight, preferably from about 2% to about 8% and more preferably from about 3% to about 6%.
In the preferred embodiment of the invention, the polymeric composition includes both at least one oxidizable polydiene and at least one metal salt catalyst, and also a platelet type nanoclay.
The composition of the invention may optionally also include one or more conventional additives whose uses are well known to those skilled in the art. The use of such additives may be desirable in enhancing the processing of the compositions as well as improving the products or articles formed therefrom. Examples of such include: oxidative and thermal stabilizers, lubricants, mold release agents, flame-retarding agents, oxidation inhibitors, dyes, pigments and other coloring agents, ultraviolet light stabilizers, organic or inorganic fillers including particulate and fibrous fillers, reinforcing agents, nucleators, plasticizers, as well as other conventional additives known to the art. Such may be used in amounts of up to about 10% by weight of the overall composition.
Suitable ultraviolet light stabilizers include various substituted resorcinols, salicylates, benzotriazole, benzophenones, and the like. Suitable lubricants and mold release agents include stearic acid, stearyl alcohol, and stearamides. Suitable flame-retardants include organic halogenated compounds, including decabromodiphenyl ether and the like as well as inorganic compounds. Suitable coloring agents including dyes and pigments include cadmium sulfide, cadmium selenide, titanium dioxide, phthalocyanines, ultramarine blue, nigrosine, carbon black and the like. Representative oxidative and thermal stabilizers include the Periodic Table of Element""s Group I metal halides, such as sodium halides, potassium halides, lithium halides; as well as cuprous halides; and further, chlorides, bromides, iodides. Also, hindered phenols, hydroquinones, aromatic amines as well as substituted members of those above mentioned groups and combinations thereof. Suitable plasticizers include lactams such as caprolactam and lauryl lactam, sulfonamides such as o,p-toluenesulfonamide and N-ethyl, N-butyl benylnesulfonamide, and combinations of any of the above, as well as other plasticizers known to the art.
Suitable fillers and extenders include fine particle size (0.01 xcexcm to 10 xcexcm) inorganic fillers, including those of platelet or granular nature, as wells as mixtures thereof. The more preferred particle sizes are in the range of 0.05 xcexcm-5 xcexcm. The most preferred particle size is in the range of 0.1 xcexcm-1 xcexcm. These fillers include mica, clay, kaolin, bentonite, and silicates, including alumina silicate. Other fine particle fillers include metal oxides, such as alumina, silica, magnesium oxide, zirconium oxide, titanium oxide. Other fine particle size include carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates including calcium sulfate and barium sulfate, as well as other materials not specifically denoted here.
Preferably the polymer compositions are produced via a melt extrusion compounding of the ethylene vinyl alcohol copolymer with the other composition components. The composition may be formed by dry blending solid particles or pellets of each of the composition components and then melt blending the mixture in a suitable mixing means such as an extruder, a roll mixer or the like. Typical melting temperatures range from about 210xc2x0 C. to about 290xc2x0 C., preferably from about 220xc2x0 C. to about 280xc2x0 C. and more preferably from about 230xc2x0 C. to about 260xc2x0 C. for the nylon blends. Blending is conducted for a period of time required to attain a substantially uniform blend. Such may easily be determined by those skilled in the art. If desired, the composition may be cooled and cut into pellets for further processing, it may be extruded into a fiber, a filament, or a shaped element or it may be formed into films and optionally uniaxially or biaxially stretched by means well known in the art.
Barrier films and articles of this invention may be produced by any of the conventional methods of producing films and articles, including extrusion and blown film techniques, bottles via extrusion or injection stretch blow molding and containers via thermoforming techniques. Processing techniques for making films, sheets, tubes, pipes, containers and bottles are well known in the art. For example, the polymer components may be preblended and then the blend fed into an infeed hopper of an extruder, or each component may be fed into infeed hoppers of an extruder and then blended in the extruder. The melted and plasticated stream from the extruder is fed into a single manifold die and extruded into a layer. It then emerges from the die as a single layer film. After exiting the die, the film is cast onto a first controlled temperature casting roll, passes around the first roll, and then onto a second controlled temperature roll, which is normally cooler than the first roll. The controlled temperature rolls largely control the rate of cooling of the film after it exits the die. Once cooled and hardened, the result film is preferably substantially transparent.
Alternatively the composition may be formed into a film using a conventional blown film apparatus. The film forming apparatus may be one which is referred to in the art as a xe2x80x9cblown filmxe2x80x9d apparatus and includes a circular die head for bubble blown film through which the plasticized film composition is forced and formed into a film xe2x80x9cbubblexe2x80x9d. The xe2x80x9cbubblexe2x80x9d is ultimately collapsed and formed into a film.
The compositions of the invention may also be used to form shaped articles through any well known process, including extrusion blow molding and injection stretch-blow molding. An injection molding process softens the composition in a heated cylinder, injecting it while molten under high pressure into a closed mold, cooling the mold to induce solidification, and ejecting the molded preform from the mold. Molding compositions are well suited for the production of preforms and subsequent reheat stretch-blow molding of these preforms into the final bottle shapes having the desired properties. The injection molded preform is heated to suitable orientation temperature in the 100xc2x0 C.-150xc2x0 C. range and then stretch-blow molded. The latter process consists of first stretching the hot preform in the axial direction by mechanical means such as by pushing with a core rod insert followed by blowing high pressure air (up to 500 psi) to stretch in the hoop direction. In this manner, a biaxially oriented blown bottle is made. Typical blow-up ratios range from 5/1 to 15/1.
Multilayered barrier articles of this invention can be formed by any conventional technique for forming films, including lamination, extrusion lamination, coinjection, stretch-blow molding and coextrusion blowmolding. The preferred method for making multilayer film is by coextrusion. For example, the material for the individual layers, as well as any optional layers, are fed into infeed hoppers of the extruders of like number, each extruder handling the material for one or more of the layers. The melted and plasticated streams from the individual extruders are fed into a single manifold co-extrusion die. While in the die, the layers are juxtaposed and combined, then emerge from the die as a single multiple layer film of polymeric material. After exiting the die, the film is cast onto a first controlled temperature casting roll, passes around the first roll, and then onto a second controlled temperature roll, which is normally cooler than the first roll. The controlled temperature rolls largely control the rate of cooling of the film after it exits the die. In another method, the film forming apparatus may be one which is referred to in the art as a blown film apparatus and includes a multi-manifold circular die head for bubble blown film through which the plasticized film composition is forced and formed into a film bubble which may ultimately be collapsed and formed into a film. Processes of coextrusion to form film and sheet laminates are generally known. Alternatively the individual layers may first be formed into sheets and then laminated together under heat and pressure with or without intermediate adhesive layers.
Optionally, an adhesive layer, also known in the art as a xe2x80x9ctiexe2x80x9d layer, may be placed between each film layer. In accordance with the present invention, suitable adhesive polymers include modified polyolefin compositions having at least one functional moiety selected from the group consisting of unsaturated polycarboxylic acids and anhydrides thereof. Such unsaturated carboxylic acid and anhydrides include maleic acid and anhydride, fumaric acid and anhydride, crotonic acid and anhydride, citraconic acid and anhydride, itaconic acid an anhydride and the like. Of these, the most preferred is maleic anhydride. The modified polyolefins suitable for use in this invention include compositions described in U.S. Pat. Nos. 3,481,910; 3,480,580; 4,612,155 and 4,751,270 which are incorporated herein by reference. Other adhesive layers non-exclusively include alkyl ester copolymers of olefins and alkyl esters of xcex1,xcex2-ethylenically unsaturated carboxylic acids such as those described in U.S. Pat. No. 5,139,878. The preferred modified polyolefin composition comprises from about 0.001 and about 10 weight percent of the functional moiety, based on the total weight of the modified polyolefin. More preferably the functional moiety comprises from about 0.005 and about 5 weight percent, and most preferably from about 0.01 and about 2 weight percent. The modified polyolefin composition may also contain up to about 40 weight percent of thermoplastic elastomers and alkyl esters as described in U.S. Pat. No. 5,139,878. Alternatively, one or more adhesive polymers may be directly blended or coextruded into other layers of the film, thus providing adhesion while minimizing the number of layers in the film.
Films produced according to the present invention may be oriented by stretching or drawing the films at draw ratios of from about 1.1:1 to about 10:1 in at least one direction, and preferably at a draw ratio of from about 1.5 to about 5 times in each in at least one direction. The term xe2x80x9cdraw ratioxe2x80x9d as used herein indicates the increase of dimension in the direction of the draw. Therefore, a film having a draw ratio of 2:1 has its length doubled during the drawing process. Generally, the film is drawn by passing it over a series of preheating and heating rolls. The heated film moves through a set of nip rolls downstream at a faster rate than the film entering the nip rolls at an upstream location. The change of rate is compensated for by stretching in the film.
Such films may be stretched or oriented in any desired direction using methods well known to those skilled in the art. The film may be stretched uniaxially in either the longitudinal direction coincident with the direction of movement of the film being withdrawn from the film forming apparatus, also referred to in the art as the xe2x80x9cmachine directionxe2x80x9d, or in as direction which is perpendicular to the machine direction, and referred to in the art as the xe2x80x9ctransverse directionxe2x80x9d, or biaxially in both the longitudinal direction and the transverse direction.
The thickness of such films according to the invention preferably ranges from about 0.05 mils (1.3 xcexcm) to about 100 mils (2540 xcexcm), and more preferably from about 0.05 mils (1.3 xcexcm) to about 50 mils (1270 xcexcm). While such thicknesses are preferred as providing a readily flexible film, it is to be understood that other film thicknesses may be produced to satisfy a particular need and yet fall within the scope of the present invention; such thicknesses which are contemplated include plates, thick films, and sheets which are not readily flexible at room temperature (approx. 20xc2x0 C.).
One noteworthy characteristic of the articles made from the compositions of this invention is that they exhibit excellent gas barrier properties, particularly oxygen barrier properties. Oxygen permeation resistance or barrier may be measured using the procedure of ASTM D-3985. In general, the films of this invention have an oxygen transmission rate (OTR) at 90% relative humidity (RH) of less than about 5.0 cm3/100 in2 (645 cm2)/24 hrs/Atm at 25xc2x0 C. using 100% oxygen, and preferably less than about 1 cm3/100 in2 (645 cm2)/24 hrs/Atm at 25xc2x0 C.
The following non-limiting examples serve to illustrate the invention. It will be appreciated that variations in proportions and alternatives in elements of the components of the invention will be apparent to those skilled in the art and are within the scope of the present invention. The examples include description of the blending processes used and analytical characterization methods employed.